Monoazo dyestuffs



United States Patent us. 01. 8-26 4 Claims ABSTRACT OF THE DISCLOSURE Monoazo dyestuffs of the formula /R1 OzN N: N\ i I I 0 A represents hydrogen, chlorine or bromine, lower alkyl, lower alkoxy, lower carbalkoxy or lower alkylsulfonyl;

Y represents lower alkoxy;

B represents the CO, -COO or S0 -group',

R represents lower alkyl;

Z represents alkylene having 2 to 4 carbon atoms;

R represents monocarbocyclic aryl-lower alkyl which may be ring-substituted by halogen, lower alkyl, or lower alkoxy; and

R represents lower alkanoyl,

as well as mixtures of such dyestuffs, are useful in the dyeing of hydrophobic organic fiber material.

The present invention concerns new, only slightly water soluble monoazo dyestuffs which can be used as dispersion dyestuffs, a process for the production thereof, processes for the dyeing of hydrophobic organic fiber material, particularly that consisting of polyglycol terephthalate, using the new dyestuffs and hydrophobic organic; fibers dyed with the aid of these dyestuffs.

The dyeing of polyglycol terephthalate fibers and fabrics in deep navy blue shades which are fag tgtsi blimation, makes the greatest demands on the'ilyestuffs used. Deep, strong dyeings having the great fastness properties required by the user can only be attained with dyestuffs which have an extraordinarily good build up and great colour strength.

Dyestuffs lacking in this respect lead to dyeings which are not fast to rubbing and, under unfavourable conditions, e.g. if tightly twisted yarns in the form of cross wound bobbins or if polyester fibres in the form of slubbing are to be dyed, lead to visible precipitations of the dyestutf.

It has now been found that in slightly water soluble monoazo dyestuffs which are suitable to attain navy blue shades on polyester fibres, which shades are fast in use, are obtained by coupling the diazonium compound of an amine of Formula I A I OzNQNHz IITO2 with a coupling component of Formula II I Z-O-Ra NHB-R (11) ice to form an azo dyestuff of Formula III In these formulas:

A represents hydrogen, chlorine or bromine, lower alkyl, lower alkoxy, lower carbalkoxy or lower alkylsulfonyl;

Y represents lower unsubstituted or non-ionically substituted alkoxy;

B represents the CO, COO or SO group;

R represents lower unsubstituted or non-ionically substituted alkyl; 1

Z represents alkylene having 2 to 4 carbon atoms;

R represents monocarbocyclic aryl-lower alkyl which may be ring-substituted by halogen, lower alkyl, or lower alkoxy;

R represents lower unsubstituted or non-ionically substituted alkanoyl.

When A is a lower alkyl, alkoxy, carbalkoxy or alkylsulphonyl group, then it is preferably the methyl or ethyl group, the methoxy or ethoxy group, the carbomethoxy or carboethoxy group, or the methylsulphonyl or ethylsulphonyl group. However, A is preferably hydrogen, chlorine or bromine. When Y is an unsubstituted lower alkoxy group then'it advantageously contains 1 to 4 carbon atoms. When this lower alkoxy group is non-ionically substituted, substituents are e.g. lower alkanoyloxy groups the alkanoyl radical of which preferably has 2. to 4 carbon atoms, e.g. the acetyloxy or propionylo'xy group; lower alkoxy groups such as the methoXy or ethoxy group; halogens such as chlorine or bromine; or the cyano group.

.Hetero atoms in Y should be separated preferably by a chain of at least two carbon atoms.

The lower unsubstituted alkyl group R'advantageously has 1 to 4 carbon atoms. If this group is non-ionically substituted, then examples of substituents are halogens such as chlorine or bromine, or lower alkoxy or alkanoyloxy groups, e.g. those mentioned in'the preceding paragraph. I

The alkylene group Z can be straigli g r ,-.'-branched chained; in the former case it is preferably-f e il-ethylene group, in the latter the 1,2-propylene or 1,2-buty1ene group.

R represents monocarbocyclic aryl-lower alkyl, preferably phenylalkyl such as a-phenyl-elhyl, fi-phenyl-ethyl, 'y-phenyl-propyl or, particularly, a benzyl group the benzene nucleus of which can contain nonionic substituents, especially halogens such as chlorine or bromine, lower alkyl groups such as the methyl or ethyl group, or lower alkoxy groups such as the methoxy or ethoxy group.

The lower unsubstituted alkanoyl group R advantageously contains 2 to 4 carbon atoms. It can contain non-ionic substituents e.g. halogen such as chlorine.

Preferably, coupling components of Formula II are used wherein Y is the methoxy or ethoxy group, B is the C0 group, R is the methyl group, Z is the group, R is the benzyl group and R is the acetyl group.

The term lower as used herein in connection with alkyl, alkoxy and alkylsulfonyl means that these radicals have 1 to 5 carbon atoms, in connection with alkanoyl, alkanoyloxy and carbalkoxy it means radicals of from 2 to 5 carbon atoms. Lower alkyl in connection with monocarbocyclic aryl means that the alkyl group may have from 1 to 3 carbon atoms.

Diazo components of Formula I which can be used 3 according to the invention are known. Examples thereof are:

1-amino-2,4-dinitrobenzene, 1-amino-2,4-dinitro-6-methylor -6-ethyl-benzene, l-amino-2,4-dinitro-6-methoxyor -6-ethoxy-benzene, 1-amino-2,4-dinitro-6-carbomethoxyor -6-carboethoxybenzene, 1-amino-2,4-dinitro-6-methylsulphonylor-6-ethylsulphonyl-benzene, or 1-amino-2,4-dinitro-6-chloroor -6-br0mo-benzene.

The coupling components used according to the invention of Formula II are obtained, for example, by reacting a compound of Formula IV I IH-BR (I with an aralkylating agent introducing R e.g. benzyl chloride, hydroxyalkylating the aralkylamino compound obtained by means of an alkylene oxide introducing a radical ZOH, e.g. with one equivalent of ethylene oxide, 1,2-propylene oxide or 1,2-butylene oxide, and acylating the N-hydroxyalkyl-N-aralkylamino compound obtained with an acylating agent introducing R such as acetyl chloride or acetanhydride. In the above, the symbols B, R, Y, Z, R and R have the meanings given for Formulae II and III. Examples of such coupling components are:

1-[N-benzyl-N-(/3-acetoxyethyl) -amino] -2-methoxy-5- acetylaminobenzene,

1- [N- 2- or 4-chlorobenzyl) -N- fl-acetoxyethyl) -amino] 2-1methoxy-5-acetylaminobenzene,

1- [N- (2- or 4-methylbenzyl) -N- (B-acetoxyethyl -amino] Z-methoxy-S-acetylaminobenzene,

1- [N- a-phenylethyl -N- B-acetoxyethyl) -amino] -2- methoxy-S-acetylaminobenzene,

1- [N- B-phenylethyl -N- fl-acetoxyethyl -amino] -2- methoxy-S-acetylaminobenzene,

1- [N- (y-phenylpropyl -N- (fi-acetoxyethyl) -amino] -2- methoxy-S-acetylaminobenzene,

1- [N-benzyl-N- S-acetoxypropyl) -amino] -2-methoxy- 5 -acetylaminobenzene,

1- [N-benzyl-N- (fl-acetoxybutyl -amino] -2-methoxy-5- acetylaminobenzene,

1- [N-benzyl-N- fl-propionyloxyethyl -amino] -2-methoxy-S-acetylaminobenzene,

1- [N-benzyl-N- fi-butyryloxyethyl) -amino] -2-methoxy- S-acetylaminobenzene,

1- [N-benzyl-N- j8-acetoxyethyl -amino] -2-ethoxy-5- acetylaminobenzene,

1- [N-benzyl-N- (,B-acetoxyethyl -amino] -2- (fi-methoxyethoxy) -5-acetylaminobenzene,

1- [N-benzyl-N- ,B-acetoxyethyl -amino] -2- fl-ethoxyethoxy) -5-acetylaminobenzene,

- 1- [N-benzyl-N- ,B-acetoxyethyl -amino -2- fl-acetoxyethoxy) -5-acetylaminobenzene,

1- [N-benzyl-N- fl-acetoxyethyl) -amino] -2- (B-chlorethoxy) -5-acetylaminobenzene,

1- [N-benzyl-N- B-acetoxyethyl) -amino] -2-rnethoxy-5- propionylaminobenzene,

1- [N-benzyl-N- fi-acetoxyethyl -amino 1 -2-methoxy-5- butyrylaminobenzene,

1- [N-benzyl-N- (,B-acetoxyethyl -amino] -2-methoxy-5- carbomethoxyaminobenzene,

1- [N-benzyl-N- B-acetoxyethyl -amino] -2-methoxy-5- carbethoxyaminobenzene,

1- [N-benzyl-N- fi-acetoxyethyl) -amino] -2-methoxy-5- carbobutoxyaminobenzene,

1- [N-benzyl-N- B-acetoxyethyl -amino] -2-methoxy-5- methylsulphonylaminobenzene, or

1- [N-benzyl-N- fi-acetoxyethyl -amino] -2-methoxy-5- butylsulphonylaminobenzene.

Cir

The coupling of the diazonium compound of an amine of Formula I with the coupling component of Formula II is preferably performed in a strong to weakly acid aqueous medium. In a strongly acid coupling, advantageous the acid is gradually buffered, e.g. with alkali metal salts of lower fatty acid.

It is advantageous to bring the dyestuffs according to the invention into a finely distributed form by milling with dispersing agents. For this purpose, anionic dispersing agents e.g. alkylaryl sulfonates, condensation products of formaldehyde with naphthalene sulfonic acids, lignin sulfonates, or non-ionogenic dispersing agents such as fatty alcohol or higher alkylphenolpolyglycol ethers, are suitable. The dyestuffs according to the invention are preferably milled with such dispersing agents with the addition of water. The resultant aqueous dyestuff pastes which contain the dyestuffs in finely distributed form can be used direct for dyeing or can be converted into non-dusty powders by careful drying by known methods.

In such forms the dyestuffs according to the invention are suitable for the dyeing of hydrophobic, organic textile fibers from an aqueous dispersion, for example for the dyeing of cellulose triacetate fibers, particularly however, for the dyeing of textile fibers made from high molecular esters of aromatic polycarboxylic acids with polyfunctional alcohols, e.g. polyglycol terephthalate, polyglycol isophthalate or polycyclohexanediol terephthalate fibers.

However, the dyestuffs can be used for the dyeing of synthetic polyamide fibers such as nylon.

In some casse, valuable dyeings can also be obtained on polyacrylonitrile fibers with the dyestuffs according to the invention.

Polyglycol terephthalate fibers are dyed with aqueous dispersions of the dyestuffs according to the invention preferably at temperatures of over C. under pressure. However, dyeing can also be performed at the boiling point of the dye liquor in the presence of carriers, e.g. alkali phenyl phenolates such as sodium-o-phenyl phenolate, 'polychlorobenzene compounds or similar auxiliaries.

The dyestuffs according to the invention have extraordinarily good afiinity to hydrophobic organic fibers, particularly to polyglycol terephthalate fibers, and on these fibers they produce level violet and especially navy blue dyeings which have very good fastness to washing, milling, sublimation, light, rubbing, perspiration, solvents, cross dyeing, decatising and industrial fumes. Especially, vegetable and animal fibers, particularly cotton, are reserved well by the dyestuffs according to the invention.

The dyestuffs according to the invention are distinguished over previously known compounds of similar constitution by extraordinarily good build up, great colour strength, stability to boiling and a wide pH-range and by the excellent fastness properties in use of the navy blue dyeings attained therewith on polyester fibers. A further advantage of the dyestuffs according to the invention is that they are suitable for the so-called thermosol dyeing process, a condition for which is high grade fastness to sublimation. In this process they also produce level, vio let and especially navy blue dyeings which are fast to rubbing. In addition, the variations in the fixing temperature which are usual under practical conditions do not noticeably affect the shade and depth of the dyeings.

Very valuable dyeings are also obtained with mixtures of dyestuffs according to the invention, particularly with mixtures which are obtained from two different diazo components usable according to the invention. Such mixtures are distinuished by very good penetration powers and, especially on polyglycol terephthalate fibres, produce very level and fast dyeings.

The following examples illustrate the invention. The temperature are given therein in degrees centigrade.

EXAMPLE 1 I OH I CHzCHzOCOCHa N O 2 NHC O OH:

37.0 g. of 1-[N-benzyl-N-(B-acetoxyethyl)-amino]-2- ethoxy-S-acetylaminobenzene are dissolved in 750 g. of

If instead of the 37 g. of 1-[N-benzyl-N-(B-acetoxyethyl)-amino]-2-ethoxy-S-acetylaminobenzene, the corresponding amount of one of the coupling components given in the following Table I is used and this is coupled under the conditions given in Example 1 with the diazonium salt solution of 1-amino-2,4-dinitrobenzene, then dyestuffs are obtained which produce dyeings on polyglycol terephthalate fibers which have similarly good properties.

TABLE I Coupling component ZOR2 NH--BR Shade on polyglycol terephthal- Number Y B R Z R; R2 ate fibers 2 OH3 -o0- -CH3 -OH2CHz om@ COCH3 Rglidish navy 3 'OCH3 -oo- CH:CH; oH1oH2- AlmQ -COCHzOl Do.

4 OCH3 -o0- -CH2CH3 oH2oH.- CH2- COCH3 Do.

5 OCzH5 -c0- CHzCHs -CH2CH1 CH2OCH3 COCH; Do.

6 -0C2H5 --C0- -CHzCHa -CH2CH2 (|]H COCH3 D0.

CH3 7 -0 02m -c0 -cm -crnon- -CH2 COCH: D0.

-CO C3H1 CH2CH2 Same as above COOH3 Do. -o0- CHzOCH3 -CH2CH2 do C0CH3 D0. -ooo- C4H9 -oH2oH2 do.- -oooH. Violet. -so=. CH3 CH2CHzdo -000H3 Reddish violet. 4402- CH: OH-. CH --do. OOOH3 Do. -CO CH CH2CHz .do. -COCHa Rglidish navy us. 14 OC3H1 o0- --CzHa -CHzCHzdo COCH3 D0. 15 0CHCH2CN -o0 -02H5 CHzCHz do COOHa Do. 16 OC4H9 --CO- C2H5 -CHzCHz (10. -COCH3 D0. 17 0CH3 00 CH2Br oH'2cH2- do o00H3 Do.

60% acetic acid. The diazonium salt solution of 18.3 g. EXAMPLE 18 1-amino-2,4-dinitrobenzene is produced by dissolving 1- C1 OON3 amino-2,4-dinitrobenzene in 100 g. of concentrated sul- 5 I I OH2 furic acid and diazotising with the amount of nitrosyl sulfuric acid corresponding to 6.9 g. of sodium nitrite. CH OCOCH This diazonium salt solution is added dropwise to the i IiIH OQCH3 2 3 above solution at 0-5. On completion of this dropwise addition, 400 g. of ice water and 100 g. of sodium acetate are added to the coupling mixture. The violet dyestulf precipitates, the composition ofwhich corresponds to the above formula, is then filtered off, thoroughly washed with water and then dried at 70-80 in vacuo. 5 g. of this dyestuff are milled with 15 g. of sodium salt of a condensation product of naphthalene-Z-sulfonic acid and formaldehyde. Polyglycol terephthalate fibers can be dyed with this dye preparation from an aqueous dispersion, optionally in the presence of a carrier such as sodiumo-phenyl phenolate, in reddish navy blue shades. The dyeings have very good fastness to rubbing, light and sublimation.

The 1 [N benzyl-N-(fi-acetoxyethyl)-amino]-2-ethoxy-5-acetylaminobenzene used in this example as cou pling component can be produced, e.g., by reacting lamino-2-ethoxy-5-acetyl-aminobenzene with benzyl chloride, adding 1 equivalent of ethylene oxide to the 1- benzylamino 2 ethoxy-S-acetylaminobenzene.obtained and then acetylating the 1-[N-benzyl-N-(fl-hydroxyethyl) -amino] -2-ethoxy-S-acetylamiuobenzene.

21.7 g. of l-amino-2,4-dinitro-6-chlorobenzene are dissolved in g. of concentrated sulfuric acid and the solution is diazotised at 20-25 with nitrosyl sulfuric acid, corresponding to 6.9 g. of sodium nitrite, for 3 hours. The diazonium salt solution so obtained is added dropwise at 0-5 to a solution of 35.6 g. of l-[N-benzyl-N-(flacetoxyethyl) amino] Z-methoxy-S-acetylaminobenzene in 850 g. of 55% acetic acid. 750 ml. of ice water and g. of sodium acetate are then added to the coupling mixture. On completion of the coupling, the greenish black dye-stuff precipitates, the composition of which corresponds to the formula given above, is filtered off, washed in the usual way with a large amount of water and dried. 10 g. of the dyestutf so obtained are brought into finely disperable form in water by milling intensively with 25 g. tion is dia zotised at 20-25 with nitrosyl sulfuric acid, of a lignin sulfonate. Polyglycol terephthalate fibers can be dyed with the preparation from aqueous dispersion, optionally in the presence of a carrier such as trichlorobenzene, in greenish navy blue shades. The dyebath is substantially exhausted. The dyeings have very good fastness to washing, rubbing, light and sublimation.

The l-[N-benzyl N B-acetoxyethyl)-amino]-2-methoxy-S-acetylaminobenzene used in this example as coupling component is obtained e.g. by condensing benzyl mixture of dyestuffs precipitates the composition of which corresponds to the two formulas given above. It is then worked up a& described in Examples 18. 10 g. of the dyestuff mixture so obtained are milled finely with 30 g. of a lignin sulfonate. Polyglycol terephthalate fibers can be chloride with 1-amino-2-methoxy-5-acetylaminobenzene, dyed with this dye preparation, optionally in the presence adding 1 equivalent of ethylene oxide to the l-benzylof a carrier such as trichlorobenzene, in navy blue shades. arnino 2 methoxy-S-acetylaminobenzene obtained and The dyebath is substantially exhausted. then acetylating the 1- [N-benzyl-N-(/3-hydroxyethyl)- When the procedure of Example 33 is repeated, but amino]-2-methoxy-S-acetylarninobenzene. 9.2 g. of 1-amino-2,4-dinitrobenzene and 10.8 g. of 1- Dyestuffs having similar properties are obtained if the amino-2,4-dinitro-6-chlorobenzene are replaced by 1.83 g. diazonium salt solution of the 1-amino-2,4-dinitro-6- of 1amino-2,4-dinitrobenzene and 23.7 g. of l-aminochlorobenzene is coupled under the conditions described 2,4-dinitro 6-brornobenzene, a dyestuff mixture is obin example 18 with one of the coupling components tained which is an excellent dyestufi' for polyglycol tergiven in the following Table II. ephthalate fibers for navy blue shades.

TABLE II Coupling component Z0R2 NH--BR Shade on polyglycol N 0. Y B R Z R1 R2 terephthalate fibers 19 O CH: -OO GH3 CHZOH2 -CH:@ C O C2}I5 Greenish navy blue.

20 -0 on; -o0- CH3 CHzCHzorn -o0o1-I2o1 Do.

21 0 on. -o 0- -CH3 CH2CHz -CHz Br -o 0 CH Do.

22 OCH3 -oo OH3 CH2CHg- CHzCHz- -o0o1-r. Do.

23 -0C2 5 CO CH:; --C 2CH2 -CH2- --COCH3 Do.

24 0 0211 -oo- 41113 -o112o1n- (I3H -o 0 on. no.

25 -0 CH3 -0 0 on., -CH;CH -om o 0 CH Do.

CHa

-O CH; C O OH2C1 -CH2CH2 Same as above D 0 CH3 -CO -CH2OCOCHa CH2CH2- do Do. -O Cal-I5 -00 O- -CH2CH2O CH: -CH2CH2 do Reddish navy blue.

--0 C2H5 -SO2 O2H5 --CH2CH2 d0 Violet. O CHzCHzCl CO-- -CH; C I2CH2 do Greenish navy blue. -0 CHzCHzOCHa -CO- CH3 CH2CHzdo Do.

32 0 CH2CHz-O -CO -CH3 'CH2CH2 .....do Do,

EXAMPLE 33 EXAMPLE 34 0 CH3 Br 0 C2H CHzCHzOOOCHa l OHZCHZO C 0 CH3 N0 NHCOCH3 N02 NH-SOzCH2 CI 26.2 g. of l-amino-2,4-dinitro-6-bromobenzene are dis- Q 1 CH2 solved in g. of concentrated sulfuric acid and, at 20-25", the solution is diazotized with nitrosyl sulfuric acid, corresponding to 6.9 g. of sodium nitrite. At O5, this diazonium salt solution is added dropwise to a solution of 40.6 g. of 1-[N-benzyl-N-(fl-acetoxyethyD- amino]-2-ethoxy-S-methylsulphonylaminobenzene in 600 g. of 50% acetic acid. 500 ml. of ice water and g. of sodium acetate are then added to the coupling mixture. On completion of the coupling, the black dyestuff precipitates, is filtered off, washed neutral with dilute sodium carbonate solution and then Washed free of salt with a large amount of water. 10 g. of the dyestuff so obtained, the composition of which corresponds to the above formula, are brought into a form which is finely dispersable in water by milling with 30 g. of lignin sulfonate. Polyglycol terephthalate fibers can be dyed with this dye preparation from aqueous dispersion, optionally in the presence of a carrier such as sodium-o-phenyl phenolate, in violet shades.

The 1-[N-benzyl-N-(B-acetoxyethyD-amino]2-ethoxy- -methylsulfonylaminobenzene used as coupling component in this example is obtained, for example, by reacting l-amino 2-ethoxy 5-methylsulfonylaminobenzene with benzyl chloride, adding 1 equivalent of ethylene oxide and then acetylating the 1-[N-benzyl-N-(fi-hydroxyethyl)-amino]-2-ethoxy 5-methylsulfony1aminobenzene obtained.

Dyestutfs having similar properties are obtained when the diazonium salt solution of l-amino 2,4-dinitro-6- bromobenzene is coupled under the conditions of Example 34 with one of the coupling components given in the following Table III.

1 0 EXAMPLE 52 0 H3 0 0 Ha I CH2CH2OCOO2Hs N 02 NH-C O-O CHzCHzO CH3 19.7 g. of 1-amino-2,4-dinitro-6 -methylbenzene are dissolved in 80 g. of concentrated sulfuric acid and the solution is diazotised at 25 with the amount of nitrosyl sulfuric acid corresponding to 6.9 g. of sodium nitrite.

43 g. of 1-[N-benzyl-N-(B-propionyloxyethyl)-amino]- 2-methoxy 5-[,B-(methoxyethoxy)-carbonylamino]-benzene are dissolved in 700 g. of glacial acetic acid and 350 g. of Water, and the solution is cooled to 0-5. The above diazonium salt solution is added dropvvise to this solution, care being taken that the temperature does not rise above 5. On completion of the dropwise addition, 200 g.

TABLE III Coupling component l ZORz NHBR Shade on polyglycol teretphthal- No. Y B R Z R1 R2 ate fibers OCH CO -CH;; -CHzCH3- OO 0 11 Greenish OH3- navy blue;

36 0C a -CO CH3 -C 2 2- Q COC2H5 Do.

37 OCH OO-- OH 0H OH -COOH3 Do;

-CHz

I OH;

38 -OCZH5 -CO- CH3 -CHzCH2 COCH3 DO.

-CH3CHCH1 39 OC lEL5 --OO -OH CH CH2 GHQ COCH Do.

40 OC H5 CO -CH; CHzCHz COOH Do.

41 -OCH3 -CO- -C2H5 CH2OH1 COCH3 D0.

42 -OCH5 CO C2H5 CH2CH2 Same as above COCH D0.

43 OCHQ CO CC1 OH OHZ do COCH Do.

44""..- OC H5 COO CzH5 -CH:CH2 do -OOCH Reddish navy blue.

45 0G;H5 COO 0H2CH2OCH2OH -CHzCHz do COCH Do.

46 a 2- a 2 2- OH Q OOCH3 Violet.

47 OCH S0z O2H5 CH2CH2- OOCH3 Do.

-CH2OH 48 OCH CH Br -C 0- CzH5 CH2OH COOH; Greenish CH navy blue.

OOH CH;,OCOCH3 CO CH; CHZCH Do. OCH2CH OOH CH ---CO -CH; 0H CHz D0. CH OO- O4H9 OH GH Do. 0CH CO O4H CHzCHz Do. 51a O0H OO- OH OH OH Do.

of sodium acetate are added to the coupling mixture and then the black dyestuff precipitate is filtered off. Its composition corresponds to the above formula. The dyestutf is thoroughly washed first with dilute sodium carbonate solution and then with water. After drying, 8 g. of the dyestuff are brought into a form which is finely dispersable in water by milling with 8 g. of the sodium salt of a condensation product of naphthalene-Z-sulfonic acid with formaldehyde and 16 g. of lignin sulfonate. Polyglycol terephthalate fibers can be dyed with this preparation from aqueous dispersion, optionally in the presence of a carrier such as sodium-o-phenyl phenolate, in navy blue shades. The dyeings have good fastness to perspiration, washing, rubbing and sublimation.

If in Example 52 the 19.7 g. of 1-amino-2,4-dinitro-6- methylbenzene are replaced by 21.3 g. of 1-amino-2,4- dinitro-6-methoxybenzene, 22.7 g. of 1-amino-2,4-dinitro- 6-ethoxybenzene, 25.5 g. of l-amino 2,4-dinitro-6-carbethoxybenzene or 24.9 g. of l-amino-2,4-dinitro-6-methylsulfonylbenzene and otherwise the procedure described in the example is followed, then dyestuffs are obtained which produce navy blue dyeings on polyglycol terephthalate fibers. The dyeings have similarly good properties.

EXAMPLE 5 3 6 g. of the dyestulf obtained according to Example 1 are dispersed in 4000 g. of water. .20 g. of sodium-ophenyl phenolate as carrier and 20 g. of diammonium phosphate are added to this dispersion and 100* g. of polyglycol terephthalate yarn are dyed for 1 /2 hours at 9598. The dyebath is substantially exhausted. The dyeing is rinsed with water and then with dilute aqueous sodium hydroxide solution and after-treated with a dispersing agent.

In this way, a reddish navy blue dyeing is obtained which is fast to washing, light and sublimation.

If in the above example, the 100 g. of polyglycol terephthalate yarn are replaced by 100 g. of cellulose triacetate fabric, dyeing is performed under the conditions given and the dyeing is then rinsed with water, then a reddish navy blue dyeing is obtained which has very good fastness to washing, light and sublimation.

EXAMPLE 54 In a pressure dyeing apparatus, 7 g. of the dyestulf obtained according to Example 18 are finely suspended in 2000 g. of water containing 4 g. of oleyl polyglycol ether. The pH of the dyebath is adjusted to 5 to 5.5 with acetic acid.

100 g. of polyglycol terephthalate fabric are introduced at 50, the bath is heated to 130 within 30 minutes and dyeing is performed for 50 minutes at this temperature. The dyeing is then rinsed with water, soaped and dried. Under these conditions, a greenish navy blue dyeing is obtained which is fast to Washing, perspiration, light and sublimation.

The dyestuffs described in the other examples produce dyeings of equal quality by this process.

EXAMPLE 55 Polyglycol terephthalate fabric (such as Dacron, Registered Trademark of E. I. Du Pont de Nemours, Wilmington, Del., U.S.A.) is pad dyed in a foulard at 40 with a liquor of the following composition:

60 g. of dyestuff mixture according to Example 33, finely dispersed in 7.5 g. of sodium alginate,

10.0 g. of coconut oil fatty acid-N,N-bis-(p-hydroxyethyl)-amide and 920.0 g. of water.

The fabric, squeezed out to a liquor content of about 100%, is dried at 100 and then the dyeing is fixed for 60 seconds at a temperature of 210. The dyed goods are rinsed with water, soaped and dried. Under these I R2 O2N- N=NN I ZOR2 N02 NHB wherein A represents hydrogen, chlorine or bromine, lower alkyl, lower alkoxy, lower carbalkoxy or lower alkylsulfonyl;

Y represents lower alkoxy;

B represents the CO, COO or SO -group;

R represents lower alkyl;

Z represents alkylene having 2 to 4 carbon atoms;

R represents monocarbocyclic aryl-lower alkyl which may be ring-substituted by halogen, lower alkyl, or lower alkoxy; and

R represents lower alkanoyl.

2. A process according to claim 1, wherein the hydrophobic organic fibers are the linear, high molecular weight esters of aromatic polycarboxylic acids with polyfunctional alcohols.

3. A process according to claim 1 wherein the hydrophobic organic fibers consist of cellulose triacetate.

4. Hydrophobic organic fibers dyed with a dyestutf of the formula wherein A represents hydrogen, chlorine or bromine, lower alkyl, lower alkoxy, lower carbalkoxy or lower alkylsulfonyl;

Y represents lower alkoxy;

B represents the CO-, COO or SO -group;

R represents lower alkyl;

Z represents alkylene having 2 to 4 carbon atoms;

R represents monocarbocyclic aryl-lower alkyl which may be ring-substituted by halogen, lower alkyl, or lower alkoxy; and

R represents lower alkanoyl.

References Cited UNITED STATES PATENTS 2,030,896 2/1936 Henshaw 260-97 2,283,211 5/1942 Jones et a1 260- 2,910,463 10/1959 Urbschat et al 260152 3,207,569 9/ 1965 Thummel 8-26 3,300,472 1/1967 Kleiman et a1 260-149 FOREIGN PATENTS 1,037,164 7/ 1966 Great Britain.

DONALD LEVY, Primary Examiner BERNARD BETTIS, Assistant Examiner US. Cl. X.R. 8-50, 55, 41 

